TW201235333A - Catalytic dehydrochlorination of hydrochlorofluorocarbons - Google Patents

Abstract

A dehydrochlorination process is disclosed. The process involves contacting RfCFClCH2X with a catalyst in a reaction zone to produce a product mixture comprising RfCF=CHX, wherein said catalyst comprises MY supported on carbon, and wherein Rf is a perfluorinated alkyl group, X = H, F, Cl, Br or I, M = K, Na or Cs, and Y = F, Cl or Br.

Description

201235333 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] The present disclosure generally relates to a hydrogen chloride reaction of a hydrochlorofluorocarbon catalyst to produce hydrofluoroolefin. More specifically, the catalyst is a metal compound supported on carbon. [Prior Art] Over the past few decades, Cold Pearl Industries has been looking for alternative refrigerants to replace the phase-out of ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) due to the Montreal Protocol. The solution for most refrigerant manufacturers is commercialized hydrofluorocarbon (HFC) refrigerant. Among the new HFC refrigerants, HFC-134a (CF3CH2F) is currently the most widely used. This refrigerant does not have the ability to destroy the ozone layer and is therefore not affected by the current regulations being phased out due to the Montreal Protocol. 15 In addition to the hidden dangers of destroying the ozone layer, global warming is another environmental concern. Therefore, there is a need for heat transfer compositions that not only reduce ozone depletion but also reduce the likelihood of global warming. Certain hydrofluoroolefins (HFOs) can meet both of these objectives. Therefore, there is a need for a hydrofluoroolefin having a lower global warming potential than existing commercial cooling products. HFO-1234yf (CF3CF=CH2) is one such hydrofluoroolefin. It will be found that hydrofluoroolefins are not only used as refrigerants, but also as solvents, sputum agents, foam expanders, detergents, push sprays, dielectrics, fire extinguishing agents and power cycle working fluids. For example, HCFO_1224yd (CF3CF=CHC1) can be used as a foam expander, fire extinguishing agent, refrigerant, and the like. SUMMARY OF THE INVENTION 25 3 5 201235333 The present disclosure provides a method of dehydrochlorination. The method includes

RfCFClCH2X contacts a catalyst in a reaction zone to produce a package 2

a product mixture of Rf € F = CHX, wherein the catalyst comprises MY supported at = 且, and its center is a perfluoroalkyl group, χ = H, F = H, Br or I ' Μ = Κ, Na or Cs and Υ = F, Cl or Br. The above general description and the following detailed description are merely illustrative and not restrictive of the invention as defined by the appended claims. Other features and benefits of one or more of the embodiments are more apparent in light of the following detailed description and claims, and the <RTIgt; </RTI> <RTIgt; Other variants are intended to cover non-exclusive inclusions. For example, a process, method, article, or device containing the plural elements listed in the list is not limited to the elements listed in the list, but may include products that are not explicitly listed but are the process 'methods' Or set other components inherent in the device. In addition, unless expressly stated to the contrary, otherwise "or" means an inclusive "or" rather than an exclusive "or". For example, any of the following cases satisfies condition A or b: a is true (or exists) and B is false (or non-existent), A is false (or does not exist) and B is true (or existing), and A and B are both true (or exist). Also, "a" or "an" is used to describe the elements and components described herein. This is done for convenience only and provides a general sense of the scope of the invention. Unless the report clearly indicates otherwise, this description should be understood to include one or at least one, and the singular also includes the plural. Unless otherwise defined, all the technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although methods or materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are still described below. Unless otherwise stated, all publications, patent applications, patents, and other references are herein incorporated by reference. In the event of a conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting. If the quantity, concentration or other value or parameter is used as a range, a preferred range or a series of larger preferred values and/or smaller preferred values, this should be considered as a specific disclosure of any larger range. Limits or preferred, all ranges formed by pairing with any smaller range of limits or preferred values, whether or not otherwise disclosed. Where a range of values is given herein, the range is intended to include the endpoints and all integers and fractions within the range, unless otherwise stated. The term "dehydrochlorination" as used herein means a method of removing hydrogen and chlorine from adjacent carbons in a die. As used herein, "fluorene smoke" means a molecule containing hydrogen, carbon, fluorine, and at least one carbon-carbon double bond. The hydrofluoroolefins disclosed herein may contain halogens other than fluorine such as chlorine, bromine and iodine. Exemplary sulphur fluorides disclosed herein include HFO-1234yf, HCFO-1233Xf, and HCFO-1224yd. 201235333 The term "alkyl" as used herein alone or in the compound word, such as "perfluoroalkyl", includes cyclic or acyclic and straight or branched alkyl such as methyl, ethyl, or Propyl, isopropyl or its different isomers. The term "perfluoroalkyl" as used herein means an alkyl group wherein 5 of all the winds have been replaced by fluorine. Examples of all-gas hospital bases include _cf3 and -CF2CF3. The term "selectivity for RjCFtCHX product" as used herein means the molar percentage of RfCF = CHX obtained in the process compared to the total moles of all of the resulting products. 10 As used herein, the term "a high temperature" means a temperature above room temperature. Disclosed is a degassing hydrogen process comprising contacting RfCFClCI^X with a catalyst in a reaction zone to produce a product mixture comprising RfCF=CHX, wherein the catalyst comprises a MY supported on carbon 15 And wherein Rf is a perfluoroalkyl group, X = η, F, a, Br or I ' Μ = K, Na or Cs and Y = F, Cl or Br. In certain embodiments of the invention, Rf is -CF3 or -CF2CF3. In certain embodiments of the invention, RfCFClCH2X is CF3CFC1CH3&amp; RfCF=CHX is CF3CF=CH2 (e.g., Rf is CF3 and X is Η). 2 In certain embodiments of the invention, 'RfCFClCH2X is CF3CFC1CH2C1 and RfCF=CHX is CF3CF=CHC1 (eg, Rf is cF3 and X is C1). Some of the hydrofluoroolefins disclosed herein, such as cf3cf==chci, are in different configurations. Isomers or stereoisomers are present. When a particular isomer 25 is not specified, it is intended that the present invention include all single conformational isomers, single stereoisomers, or any combination thereof. For example, 201235333 HCFO-1224yd (CF3CF=CHC1) represents the f isomer, the oxime isomer or any combination thereof or any mixture of the two isomers. Starting materials for the dehydrogenation process of the present disclosure, such as RfCFClCH2X, can be synthesized by methods known in the art. For example, as described in European Patent Publication EP 2 135 855, HCFC-244bb (CF3CC1FCH3) can be prepared by contacting HCFO-1233xf (CF3CCl=CH2) with HF in the presence of a catalyst having about 25 to about 99.9 mole percent of antimony pentachloride and about 0.1 to about 75 mole percent of the metal of Lewis acid. In another example, ίο HCFC-234ba (CF3CC1FCH2C1) can be prepared by the reaction of HFO-1234yf with Cl2 or by the addition reaction of CF2=CFC1 with ch2fci. The dehydrochlorination process can be carried out in the liquid phase or in the vapor phase using well-known chemical measures, including chemical, continuous, semi-continuous or batch operations. The temperature in the reaction zone is usually from about 200 ° C to about 500 ° C. In some of the embodiments of the invention, the temperature in the reaction zone is from about 320 ° C to about 380 ° C. 5 Xuan degassing enthalpy method can be carried out under super atmospheric pressure pressure, atmospheric pressure or sub-atmospheric pressure. The contact time of the starting material RfCFClCI^X with the catalyst can vary widely. The contact time is usually from about 10 seconds to about 150 seconds. In some embodiments of the invention, the contact time is from about 40 seconds to about 10,000 seconds. The contacting step of the present invention can be carried out by methods known in the art. In some embodiments of the invention, the starting material (10) is now selectively and with an inert gas fed to the reactor containing the catalyst. In certain embodiments of the invention, the starting material RfCFClCH2X is selectively passed 25 with an "inert gas" through the catalyst bed of the reactor (10). In some of the present inventions 201235333 $ =, the starting material RfCFC1CH2x is selectively coupled to the same inert;; ^ should be mixed with the catalyst in a stirring or agitating manner. The =II hydrogenation process can be carried out in an inert gas such as %, heart or N2. In certain embodiments of the invention, the inert gas is co-fed to the reaction vessel with the starting material. The heart (4) provides a catalyst suitable for degassing hydrogen. The contact /, ^ &gt; 3 is further loaded on the carbon by the metalloid salt represented by the formula Μγ, wherein ^ or 丫^^ or ^ is a certain KF in the present invention. In certain embodiments of the invention, Μ.Υ is KC1 〇 and the alkali metal _ salt can be deposited on the support using deposition techniques well known in the art. For example, the metal halide salt can be dissolved in deionized water&apos; and then mixed with freshly dried pickled activated carbon. The mixture is mild and scrambled until the solution of the metal tooth salt is completely absorbed by the activated carbon. Thereafter, the supported activated carbon is dried at a high temperature and stored in a sealed container for use as a catalyst. In certain embodiments of the invention, the contact comprises a metal halide salt of from about 5 wt% (by weight percent) to about 40 wt0/Torr, based on the total of the alkali metal halide salt and carbon. In certain embodiments of the invention, the ruthenium catalyst contains from about 1 〇 wt 〇 / 至 to about 30 重量 % of an alkali metal halide salt based on the total of the alkali metal halide salt and carbon. The carbon used in the examples of the present invention may be derived from any of the following sources: wood, peat, coal, coconut shell, bone, lignite, petroleum-based residues, and sugar. Commercially available carbons that can be used include those sold under the trademarks Barneby &amp; SutcliffeTM, DarcoTM, Nucharm, Columbia JXNtm® Columbia LCKTM, CalgonTM 25 201235333 PCB, CalgonTM BPL, Westvaco' NoritTM, TakedaTlv^

Barnaby Cheny NBTM. The carbon also includes a three-dimensional matrix pore carbonaceous material. Examples are described in U.S. Patent No. 4,978,649. In a fifth embodiment of the present invention, the carbon includes a three-dimensional space matrix carbonaceous material which can be obtained by introducing a gaseous or vaporous carbonaceous compound such as a hydrocarbon into a large amount of carbonaceous material ( For example, carbon black particles; the carbonaceous compound is decomposed to deposit carbon on the surface of the particles; and the resulting material is treated with an activator gas comprising steam to provide a porous carbonaceous material. A carbon-carbon composite ίο is formed as a result. Carbon includes unwashed carbon and acid washed. In certain embodiments of the invention, a suitable catalyst can be made by treating the carbon used as a catalyst-supported carrier with an acid.

The acid is, for example, HN〇3, HCBu HF, H2S04, HC104, CH3C00H and combinations thereof. The acid treatment is usually sufficient to provide carbon containing less than 1 〇〇〇卯 ash 15 points. Some suitable carbon acid treatments are described in U.S. Patent No. 5,136,113. In certain embodiments of the invention, an activated carbon is dried at a high temperature and then impregnated for 8 to 24 hours with occasional stirring in 1 to 12 weight percent of HN〇3. The impregnation method can be carried out at a temperature ranging from room temperature to 80 °C. The activated carbon is then filtered and washed with deionized 20 water until the pH of the wash liquor is greater than 4.0 or until the pH of the wash liquor is constant. Finally, the activated carbon is dried at a high temperature. In certain embodiments of the invention, the carbon is an activated carbon. In certain embodiments of the invention, the carbon is a pickled activated carbon. The carbon may be in the form of a powder, a granule or a pellet. 25 The effluent from the reaction zone usually includes residual starting material

RfCFCICHaX, the desired hydrofluoroolefin product RfCF=CHX and some 9 201235333 by-products. The desired product, RfCF = CHX, can be recovered from the product mixture by conventional methods. In certain embodiments of the invention, the product RfCF=CHX can be purified or recovered by distillation. Through experiments, it was found that the catalyst dehydrochlorination method of the present invention produces a desired product having a surface selectivity. In certain embodiments of the invention, the product selectivity to ' RfCF = CHX is at least 90 mole %. In certain embodiments of the invention, the product selectivity to RfCF = CHX is at least mol%. In certain embodiments of the invention, catalyst activity may decrease as the dehydrochlorination 10 process continues. It has been found through experiments that the catalyst can be regenerated by inert gas flushing or the activity of the catalyst can be restored. Therefore, in an embodiment of the invention, the method of dehydrogenating hydrogen further comprises washing the catalyst with an inert gas. The inert gas can be selected from the group consisting of He, Ar, A, and any combination thereof. In certain embodiments of the invention, the dehydrochlorination process further comprises flushing the catalyst with N2. The method of rinsing can be accomplished by passing an inert gas through the catalyst at a high temperature. In certain embodiments of the invention, the temperature is from about 2 ° C to about 500 ° C. In certain embodiments of the invention, the temperature is from about 32 ° C to about 380 ° C. In certain embodiments of the invention, the temperature in the rinsing process 20 is about the same as the temperature in the dehydrochlorination stage. In some embodiments of the invention, the flow rate of the inert gas during the flushing process is from about 5 times to about 50 times the flow rate of the RfCFClCi^X in the degassing hydrogen phase. In certain embodiments of the invention, the flow rate of the inert gas during the rinsing process is from about 1025 to about 30 times the flow rate of the RfCFClCH2X during the dehydrochlorination stage. The rinsing time varies depending on the recovery rate of the catalytic activity. The rinsing time is usually from about 1 hour to about 12 hours. 201235333 During the rinsing process, the starting material RfCFClCI^X is typically stopped feeding into the reactor. In certain embodiments of the invention, upon detection of a significant decrease in catalyst activity, RfCFClCHzX flowing into the reactor is interrupted and replaced with an inert gas, and the inflow rate of the inert gas is from about the previous RfCFClC^X inflow rate. 5 times to about 50 times' while the temperature of the reactor remains unchanged. When the flushing process is finished, the inert gas for flushing is interrupted and the inflow of RjCFCICHzX is restarted. The reactor, distillation column and its associated supply pipe, effluent pipe and associated unit used in the process of the embodiment of the present invention may be constructed of a corrosion resistant material. Typical constituent materials include TeflonTM and glass. Typical constituent materials also include stainless steel (especially austenitic), well-known high nickel alloys such as: MonelTM nickel-copper alloy, HastelloyTM nickel base alloy and inc〇neiT]v^chromium alloy and copper clad steel. . The various aspects and embodiments described above are illustrative only and not limiting. After reading this specification, those skilled in the art will appreciate that other aspects and embodiments may be possible without departing from the scope of the invention. EXAMPLES The concepts described herein are further illustrated by the following examples, which are not intended to limit the scope of the invention described in the claims. Preparation of hno3 Washed Carbon 2 An active barrier (having a surface area ranging from about 丨2 Torr to about 1500 m/g) was immersed in an aqueous solution of i% by weight for 12 hours at room temperature, after which it was removed. The ionized water was completely washed and dried at i2〇201235333 C for 12 hours. Some of the HN〇3 wash activated carbon prepared above was loaded with KF and used as an example, and some were loaded with KC丨 and used in Examples 2 and 3. 5 HN〇3 Washed TakedaTlv^&gt;^ Preparation of TakedaTM activated carbon (having a surface area ranging from about 丨〇〇〇m2/g to about 1200 m2/g) at room temperature at 1 wt% HN The hydrazine 3 aqueous solution was allowed to stand for 12 hours, after which it was completely washed with deionized water and dried at 120 ° C for 12 hours. The hn〇3 wash TakedaTM carbon was then loaded with ίο KC1 and used in Examples 4 and 5. Preparation of HN〇3 Washed Takeda11^^^ The TakedaTM activated carbon (having a surface area ranging from about 10 〇〇m 2 /g to about 1200 m 2 /g) was immersed at 8 ° 〇 / 0 at 6 ° ° C 15 HN〇3 in water for 12 hours, after which it was completely washed with deionized water and dried at 120 ° C for 12 hours. The TakedaTM carbon prepared above was then loaded with KC1 and used in Example 7. Example 1 20 Example 1 illustrates the contact of HCFC-244bb with KF supported on pickled activated carbon to produce HFO-1234yf. 10 cc (cubic centimeters) of 20 wt% KF/acid washed activated carbon catalyst particles were loaded into a 0.43 吋I. D. MonelTM reactor tube to form a catalyst bed. A gaseous mixture of 98.8 mole % HCFC-244bb and 1.2 mole % 25 HCFO-1233xf (CF3CC1 = CH2) was passed through the catalyst bed at a rate of 1.1 g/hr along with 4.3 ml/min of N2. Back pressure is about atmospheric 12 201235333 Pressure. The effluent from the reactor tubes was analyzed by GC and GC-MS. The conversion of the starting material HCFC-244bb and the product selectivity to HFO-1234yf are summarized in Table 1 below, which shows good product selectivity to HFO-1234yf over a wide range of temperatures. Table 1 Conversion selectivity temperature °c Molar percentage of mole % ___ HCFC-244bb HFO-1234yf 225 14.86 91.89 230 14.36 91.16 279. 28.03 94.19 275 15.52 92.15 _ 327 23.49 94.63 _ 329 7.63 87.86 377 41.09 96.52 377 54.62 97.80 375 57.82 97.89 374 65.63 98.22 . 376 72.83 98.19 390 82.75 96.28 403 —---- 89.60 ^ 98.04 _ 399 88.39 97.45 427 96.33 96.43 424 96.03 95.32 The stability of the catalyst is about 385 ° C under the same method conditions as described above. test. At the end of each hour, the effluent from the reactor tubes was analyzed by GC and GC-MS. The results are shown in Table 2 below. Table 2 Percentage of converted Mohrs in hours HFC-244bb Percentage of selective molars HFO-1234vf — 1 82.81 95.90 13 201235333 2 77.78 96.13 3 76.91 96.36 4 72.82 96.31 5 73.07 96.10 6 74.47 96.06 7 70.06 95.72 8 72.07 96.22 9 70.70 96.01 10 69.04 96.45 11 70.57 96.27 Example 2 Example 2 illustrates the contact of HCFC-244bb with KC1 supported on pickled activated carbon to produce HFO-1234yf. 10 cc of 25 wt% KC1/acid washed activated carbon catalyst particles were loaded into a 0.43 吋I.d. MonelTM reactor tube to form a catalyst bed. A gaseous mixture of 99.7 mole % HCFC_244bb and ο mole % HCF 〇_1233xf was passed through the catalyst bed at a rate of 1.1 g/hr along with 4.3 ml/min N2. The back pressure is about atmospheric pressure. The effluent from the reactor tubes was analyzed by GC and GC-MS. The conversion of the starting material HCFC-244bb and the product selectivity to HFO-1234yf are summarized in Table 3 below, which shows good product selectivity to HFO-1234yf over a wide range of temperatures. Table 3 Temperature °c Conversion Mohr Percentage ΤΤΓ'Ρ'Γ'-ΟΛ/ΙΚΚ Selectivity Mohr Percentage HFO-1234yf

201235333 386 89.99 97.80 1 385 90.78 97.57 396 93.28 97.14 403 -7^--- 95.23 96.89 427 96.80 -:----_ 98.27 423 98.01 96 80 The stability of the catalyst is about the same method conditions as described above. Test at 385 ° C. At the end of each hour, the effluent from the reactor tubes was analyzed by Gc and GC_MS. The results are summarized in Table 4 below. Table 4 Time Hours

Selectivity Mohr percentage HF〇-1234yf ~^7 80~9TJT Conversion Mohr percentage HCFC-244bb

90.78 90.80 97.83 91.401ΠΪ 91.27 89.45 97.63 T7.61

97.82 ~9TM 89.65 97.83

Example 3 Example 3 illustrates that the carbon-loaded K C1 catalyst works well under high back pressure. All process conditions were the same as in Example 2 except that the back pressure was 45 psig (pounds per square foot). The analysis of the effluent from the reactor piping is shown in Table 5 below.

S 15 201235333 Table 5 Temperature °c Conversion Mohr Percent HCFC-244bb Selectivity ~~ Mohr Percentage HFO-1234yf 353 43.72 98.88 351 27.41 98.50 . 375 52.28 98.14 374 50.17 98.17 401 77.89 96.75 425 89.94 95.05 ~ Example 4

5 Example 4 illustrates the contact of HCFC-234ba with KC1 supported on pickled TakedaTM carbon to produce HCF (M224yd. Load 10 cc of 25 wt% KC1/acid washed TakedaTM carbon catalyst particles into 0.43 吋I. D· A catalyst bed was formed in the MonelTM reactor tube. A 10 gaseous mixture of 96 mole % HCFC-234ba and 4 mole % HFO-1234yf was passed through the catalyst bed at a rate of 1.1 g/hr along with 4.3 ml/min N2. The back pressure is about atmospheric pressure. The effluent from the reactor tube is analyzed by GC and GC-MS. The conversion of the starting material HCFC-234ba and the product selectivity to HCFO-1224yd are shown in Table 6 below. Wide range of high conversion of HCFC-234ba and good product selectivity for 15 HCFO-1224yd. Table 6 Temperature °C Conversion Mohr Percent HCFC-234ba Selective Molar Percentage trans-HCFC-1224yd Selective Molar Percentage cis-HCFC-1224vd 241 70.73% 90.96% 7.05% 247 74.04% 91.03% Γ 6.81% 201235333 275 99.90% 89.29% 5.98% 275 99.88% 88.32% _ 6.23% 295 100.00% 93.57% 5.00% 302 100.00% 93.47% _ 5.04% 318 100.00% 91.64% 5.36% 325 100.00% 92.13% 5.53% 350 100.00% 91.67% 6 .20% 350 100.00% 90.52% - 613% 373 100.00% 84.62% 6.40% Example 5 Example 5 illustrates that N2 flushing allows carbon to be regenerated by the loaded KC1 catalyst to restore the conversion of the starting material HCFC-244bb. 25 wt% KC1/acid washed TakedaTM carbon catalyst particles were loaded into a 0.43 吋ID MonelTM reactor tube to form a catalytic bed. A gaseous mixture of 99.4 mol% HCFC-244bb and 0.6 mol% HCFO-1233xf was The rate of 1.1 g/hr, along with 4 3 ml/min of N2, passes through the catalyst bed. The back is about atmospheric pressure. The effluent from the reactor tube is analyzed by GC and GC-MS. The stability of the catalyst is about At 350 ° C. It was found that after 113 hours of operation, the conversion of HCFC-244bb decreased from about 40 mole % to about 25 mole %. The influx of HCFC-244bb/HCFO-1233xf/N2 through the catalyst bed was interrupted, and then the catalyst was flushed at 150 ° C for 150 seem (standard cubic centimeters per minute) of N2 for 3 hours. After the rinsing, the inflow of HCFC-244bb/HCFO-1233xf/N2 was restarted, and it was found that the conversion rate returned to about 38 mol%. Product selectivity to HFO-1234yf consistently at about 95 mol% water f during the total 130 run hours test. The result is shown in Figure 1. 17 5 20 201235333 Example 6 Example 6 illustrates the contact of HCFC-244bb with KC1 supported on unwashed activated carbon to produce HFO-1234yf. 10 cc of 25 wt% KC1/Unwashed Calgon Carbon COCO Plus (-activated carbon 'with surface area ranging from about 900 m2/g to about 1200 m2/g) of catalyst particles (6 to 10 mesh) A catalyst bed was formed in a 0.43 吋I.D. Monel reactor tube. A gaseous mixture of 99.7 mol% of HCFC-244bb and 〇_3 mol% of HCFO-1233xf was passed through the catalyst bed at a rate of 1.1 g/hr along with 4 3 ml/min of hydrazine. The back pressure is about atmospheric pressure. The effluent from the reactor tubes was analyzed by GC and GC-MS. The conversion of the starting material HCFC-244bb and the product selectivity to HFO-1234yf, together with the run time series, are given in Table 7 below. Time temperature ec conversion selectivity hour molar percentage of moles ^- ~~ΤΓ5 ------HCFC-244bb HFO-1234yf __ 1 -^_J6.91% 90.52% 2 ,—▲ 373 ----- 54.45% 96.77% 3 402 -^_82.28% 98.43% _ 4 386 ---- 73.00〇/〇98.22% 5 384 -^___71.59% 97.68% 6 ------ 386 ----- ----- 96.79% 7 一11一386 -__72.11〇/〇97.09% 8 387 -__73.77% 96.84% 9 -----, Λ 385 ----69.60% 96.85% __ 10 387 96.22% __ ---,1 423 ----,U.U4% 11 ---__84.52% 85.46% 12 One--:_ 424 -79.81% 84.46% 13 394 —______ 58.46% 86.95% 14 401 ----61.35% 86.95% 15 401 ----57.46% 86.40% 18 201235333 16 398 53.38% 87.35% 17 401 53.58% 86.78% 18 401 52.17% 86.61% 19 394 41.79% 88.88% 20 402 48.86% 87.50 % 21 401 42.71% 88.54% 22 398 39.89% 89.01% Example 7 Example 7 illustrates the HCC-244bb with 5 wt% KC1/ pickling

TakedaTM carbon contact produces HFO-1234yf. 5 Load 10 CC of 5 wt% KC1/acid washed TakedaTM carbon catalyst particles (6 to 10 mesh) into a 0.43 吋I, D, MonelTM reactor tube to form a catalytic bed. A gaseous mixture of 99.7 mole % HCFC-244bb and 0.3 mole % HCFO-1233xf was passed through the catalyst bed at a rate of 7.3 seem. The back pressure is about atmospheric pressure. The effluent from the reactor tube was analyzed by GC and GC-MS. The conversion of the starting material HCFC-244bb and the product selectivity to HFO-1234yf, along with the temperature and run time series are shown in Figure 2. The catalyst exhibited good selectivity to HF〇-1234yf (still at 90% by mole) and good stability at 325^. It should be noted that not all of the 15 actions described above in the general description or examples are necessary, some of the specific actions may not be necessary, and one or more other actions may be performed in addition to the actions described. . Moreover, the order of the actions listed is not necessarily the order in which the steps are performed. The concept of a particular embodiment has been described in the above description. However, one of the four general practitioners of the art understands that various modifications can be made without departing from the invention of the invention described in the π patent fe® 201235333. Accordingly, the description is to be regarded as illustrative and not restrictive, and all such modifications are included in the scope of the invention. The ribs have been described with respect to the benefits, other advantages, and problem solutions of a particular embodiment. However, benefits, advantages, problem solving, and any features that would make these benefits, advantages, or problem solutions more important are not interpreted as critical, necessary, or essential features of any or all patent applications. - It should be understood that, for clarity of description, the various embodiments described herein, broadly, and in some aspects may also be combined in a single embodiment in the same manner as in the drawings. Example 5 is a graphical representation of the selectivity of the product of HCFC_244bb HKM234yf after the catalyst was dechlorinated and the catalyst was purged with nitrogen. The conversion rate and Dong Yuguo's = purely described in (4) 7's job Qiancheng branch analysis [main component symbol description] 20

Claims (1)

201235333 VII. The scope of the patent application: 1. A method for dehydrochlorination comprising the step of bringing RfCFC][CH2X into contact with a catalyst in a region to produce a product mixture comprising RiCF=CHX, wherein the S-catalyst comprises MY carried on carbon, and wherein Rf is a perfluoroalkyl group, 5 X Η, F, C1, Br or I ' M = K, Na or Cs and Y = F, C1 or Br 〇 2. The method of dehydrochlorination of item 1, wherein the carbon is an activated carbon. Ίο 3. The method for dehydrogenating hydrogen as described in claim 2, wherein the carbon is acid-washed activated carbon. The method for dehydrogenating hydrogen as described in Item 1 wherein the temperature of the reaction zone is from about 200 t to about 5 Torr (rc. 6·^). The method for dehydrogenating hydrogen according to item 5, wherein the 20 series in the reaction zone is from about 32 (TC to about 38 (rc. ^), the method of dehydrochlorination described in claim 1, wherein the product of RfCF=CHX The selectivity is at least % Mohr. 25 8. The method of dehydrochlorination as described in request jg 1 , . , , wherein the product selectivity for RfCF=CHX is at least 96 mol%. S 21 201235333 9. The method of dehydrochlorination according to Item 1, wherein RfCFClCH2X is CF3CFC1CH2C1 and RfCF=CHX is CF3CF=CHC1. 5. The dehydrochlorination method according to claim 1, wherein RfCFClCH2X is CF3CFC1CH3 and RfCF=CHX is CF3CF=CH2. The method of dehydrochlorination according to claim 1, further comprising rinsing the catalyst with an inert gas. 〇12. The degassing argon method according to claim 11, wherein the inert gas is N2.